阅读说明：本技术 一种兼具电磁屏蔽、耐紫外线的高性能柔性防弹材料的制备方法 (Preparation method of high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance ) 是由 楚艳艳 黄伟韩 何浩南 温路娉 陈思楠 李欣 刘春晖 高龙 喻红芹 何建新 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种兼具电磁屏蔽、耐紫外线的高性能柔性防弹材料的制备方法,所述的方法包括如下步骤：1)织物的预处理；2)纳米线在织物上的成核；3)纳米线在织物上的生长。所述的织物为长丝纱线机织物。所述的纳米线为氧化锌纳米线。本发明实现了在保持原有材料重量增加低于5%的情况下,在克重为1.0g的圆柱形子弹速度为475m/s的冲击速度下,其处理后的试样的能量吸收性能比未整理的原布提高了10-25%,单层织物对高频和低频波段屏蔽可达到：59%和45%。按AATCC186耐紫外线性照射后的力学性能仍能保持95%以上。(The invention discloses a preparation method of a high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance, which comprises the following steps: 1) pretreating the fabric; 2) nucleation of nanowires on the fabric; 3) growth of nanowires on the fabric. The fabric is a filament yarn woven fabric. The nano wire is a zinc oxide nano wire. The invention realizes that under the condition of keeping the weight increase of the original material to be less than 5 percent and the impact speed of 475m/s of the cylindrical bullet with the gram weight of 1.0g, the energy absorption performance of the processed sample is improved by 10 to 25 percent compared with that of the original cloth without finishing, and the shielding of the single-layer fabric on high-frequency and low-frequency wave bands can reach the following conditions: 59% and 45%. The mechanical property of the AATCC186 after ultraviolet radiation resistance can still be kept above 95 percent.)

1. A preparation method of a high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance is characterized by comprising the following steps:

(1) preparing raw cloth: the experimental cloth is a fabric with the warp and weft density of 9 pieces/cm;

(2) pretreatment of the fabric: putting the fabric into boiling scouring liquid, scouring for 30 minutes to remove impurities, taking out and putting into a drying oven for drying for later use;

(3) nucleation of nano zinc oxide on aramid fabric: respectively heating the ethanol solution of sodium hydroxide and the ethanol solution of zinc acetate to 40-90 ℃, then uniformly mixing to obtain a mixed solution, putting the fabric pretreated in the step (2) into the mixed solution for 10-60 minutes, taking out the fabric and padding the fabric on a padder, adhering colloidal suspension zinc oxide nanoparticles on single fibers to form zinc oxide nucleation sites, adopting a two-dipping and two-rolling process, and then baking the fabric for 10 minutes at the temperature of 100-180 ℃;

(4) growth of zinc oxide nanowires: and (3) heating the growth solution in a sealed manner, placing the aramid fiber fabric treated in the step (3) in the growth solution at the temperature of 50-95 ℃, stirring for 0.5-5 hours in a sealed convection furnace, taking out the fabric after the aramid fiber fabric is treated by the growth solution, rinsing the aramid fiber fabric with distilled water, and then drying the aramid fiber fabric in a blast dryer.

2. The preparation method of the high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance according to claim 1, is characterized in that: the fabric in the step (1) is aramid fiber fabric, carbon fiber fabric, ultra-high performance polyethylene fabric, polyether ether ketone fiber fabric, basalt fiber fabric and poly-p-phenylene benzobisoxazole fiber fabric, and the yarn fineness is 1000 deniers.

3. The preparation method of the high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance according to claim 1, is characterized in that: the boiling-off liquid in the step (2) is composed of chloroform, acetone and ethanol according to the volume ratio of 1:1:1-1:1: 10.

4. The preparation method of the high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance according to claim 1, is characterized in that: in the step (3), the concentration of the ethanol solution of sodium hydroxide is 0.005-0.02 mol/L, the concentration of the ethanol solution of zinc acetate is 0.005-0.025mol/L, and the volume ratio of the ethanol solution of sodium hydroxide to the ethanol solution of zinc acetate is 2: 1.

5. The preparation method of the high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance according to claim 1, is characterized in that: the growth solution in the step (4) comprises the following components: 10-70mmol/L zinc nitrate hexahydrate, 5-40mmol/L hexamethylenetetramine, 2-14mmol/L polyethyleneimine and 0.1-2mol/L ammonia water.

Technical Field

The invention belongs to the technical field of manufacturing of body armor, and relates to a nano surface treatment technology which can improve the bulletproof performance of a fabric on the premise of not increasing the weight of the fabric. In particular to a surface treatment technology for controlling the surface friction of the fiber to improve the bulletproof performance of the bulletproof fabric. In particular to a method for growing nano wires on the surface of a fabric, roughening the surface of the fiber of the fabric, controlling the friction force among yarns, improving the bulletproof performance of a bulletproof fabric, and simultaneously playing roles in resisting ultraviolet aging and absorbing electromagnetic waves.

Background

Body armor, also called bullet proof vests, is common in both police law enforcement operations and military operations, where individual soldiers are matched and used with body armor. As an important individual protective device, body armor has become the life guard of the user. Can prevent bullets without influencing the free movement of the wearer, and is an ideal requirement of the bulletproof clothes. Body armor is generally classified into hard body armor, soft body armor, and soft and hard composite body armor according to the level of protection. The soft body armor is highly concealed, lightweight and flexible, and is very suitable for policemen, security personnel or administrative demanders to wear daily. The UD laminated cloth is widely applied in the existing soft body armor material, and the main reason is that the UD laminated cloth is unidirectionally arranged in each layer of fiber and can instantly expand the shock wave generated by a bullet. However, the UD laminate is essentially a composite material of fibers and polyethylene resin, and is poor in flexibility and air permeability and low in wearing comfort. In recent years, two-dimensional fabrics woven directly from high-performance fiber yarns have received much attention as ballistic materials. As a traditional textile material, the two-dimensional fabric has mature weaving technology, wide and high air permeability, soft structure and comfortable wearing. The ballistic performance of two-dimensional fabrics woven with high-strength fibers such as UHMWPE fibers, aramid fibers and the like is inferior to UD fabrics. How to improve the bulletproof performance of high-performance fiber woven fabrics is a precondition for developing comfortable bulletproof fabrics.

The factors influencing the bulletproof performance of fabric body armor are many, wherein the friction force among yarns is one of the main factors. A large number of numerical simulation studies show that the increase of the friction force between yarns is helpful for improving the bulletproof performance of the fabric. Based on the guiding thought, the key for improving the bulletproof performance of the fabric body armor is to improve the friction force among yarns. The friction force among the yarns is improved on the premise that the volume and the weight of the yarns are not remarkably increased, and the mechanical property of the yarns is not influenced. Methods for increasing the friction between yarns are chemical agent methods, shear thickeners, etc., but these methods increase the friction and also increase the weight of the ballistic fabric significantly. Patent [ ZL201711048786.4] changes the friction between yarns by sol-gel nanotechnology and plasma vapor deposition, and although the friction between yarns is improved to some extent, the increase is far from sufficient. The nano-wire has large surface area, and can generate mechanical locking when growing on the surface of the fiber during the friction between the fibers, increase the friction energy consumption and finally increase the energy absorption of the fiber in the ballistic impact process.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method of a high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance, and the protection performance of the high-performance flexible bulletproof material is improved on the premise of not increasing the weight of a fabric soft bulletproof layer. The bulletproof layer fabric is processed by adopting a nanowire oxide technology. Through the bulletproof performance test, under the impact action of a cylindrical bullet with the weight of 1.0g and the impact speed of 475m/s from the normal direction of the fabric surface, the energy absorption of the single-layer fabric after impact is increased by 10-25% compared with the fabric before treatment, and the weight increase rate is within 5%.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a high-performance flexible bulletproof material with electromagnetic shielding and ultraviolet ray resistance comprises the following steps:

(1) preparing raw cloth: the experimental cloth is a fabric with the warp and weft density of 9 pieces/cm;

(2) pretreatment of the fabric: putting the fabric into boiling scouring liquid, scouring for 30 minutes to remove impurities, taking out and putting into a drying oven for drying for later use;

(3) nucleation of nano zinc oxide on aramid fabric: respectively heating the ethanol solution of sodium hydroxide and the ethanol solution of zinc acetate to 40-90 ℃, then uniformly mixing to obtain a mixed solution, putting the fabric pretreated in the step (2) into the mixed solution for 10-60 minutes, taking out the fabric and padding the fabric on a padder, adhering colloidal suspension zinc oxide nanoparticles on single fibers to form zinc oxide nucleation sites, adopting a two-dipping and two-rolling process, and then baking the fabric for 10 minutes at the temperature of 100-180 ℃; the dried aramid fabric containing the seed layer is used as a growth substrate of the zinc oxide nanowire;

(4) growth of zinc oxide nanowires: and (3) heating the growth solution in a sealed manner, placing the aramid fiber fabric treated in the step (3) in the growth solution at the temperature of 50-95 ℃, stirring for 0.5-5 hours in a sealed convection furnace, taking out the fabric after the aramid fiber fabric is treated by the growth solution, rinsing the aramid fiber fabric with distilled water, and then drying the aramid fiber fabric in a blast dryer.

Further, the fabrics in the step (1) are aramid fabrics, carbon fiber fabrics, ultra-high performance polyethylene fabrics, polyether ether ketone fabrics, basalt fiber fabrics and poly-p-phenylene benzobisoxazole fiber fabrics, and the fineness of the yarns is 1000 deniers.

Further, the boiling-off liquid in the step (2) is composed of chloroform, acetone and ethanol according to the volume ratio of 1:1:1-1:1: 10.

Further, in the step (3), the concentration of the ethanol solution of sodium hydroxide is 0.001-0.02mol/L, the concentration of the ethanol solution of zinc acetate is 0.001-0.025mol/L, and the volume ratio of the ethanol solution of sodium hydroxide to the ethanol solution of zinc acetate is 2: 1.

Further, the composition of the growth solution in the step (4) is as follows: 10-70mmol/L zinc nitrate hexahydrate, 5-40mmol/L hexamethylenetetramine, 2-14mmol/L polyethyleneimine and 0.1-2mol/L ammonia water (28-30 wt%).

The invention has the beneficial effects that: the finishing process is simple, and the bulletproof fabric after finishing is remarkably improved in bulletproof performance under the condition that the weight of the original material is slightly increased. Carrying out non-penetrability experiments on aramid cloth treated by different processes and untreated aramid cloth, wherein the bullet for the experiments is cylindrical, the weight is 1g, the height and the diameter are both 5.5mm, the impact speed is 475m/s, the energy absorption amount can be increased by 10-25%, and the weight increase rate is lower than 5%; meanwhile, the shielding of the single-layer fabric on high-frequency and low-frequency wave bands can be achieved at the same time: 59% and 45%. The mechanical property of the AATCC186 after ultraviolet radiation resistance can still be kept above 95 percent.

Drawings

Figure 1 is the appearance of the surface of the finished aramid fabric.

Detailed Description

The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.